Catalyzer for hydrogenating oils and the like.



1 No Drawing".

' which To all whom it may concern:

' Be it known'that I, MARTIN HILL IT'rNER, a citizen of the United States, residing in Jersey City, Hudson county, State of New Jersey, have invented certain new and useful Improvements in Catalyzers for Hydrogenating Oils and the like; and I do hereby declare the following to be a full, and exact description of the invention, such as will enable others skilled in the art to it appertains to make and use the same.

My invention relates to certain new and useful improvements in catalyzers, for use in the hydrogenation of oily material contaming unsaturated bodies as, for instance,

fatty acids and their esters.

It is based upon the discovery that charcoal, which has deposited, throughout its structure a small amount of certain mineral bodies, as, for example, certain compounds of the'earth metals or alkaline earth metals, such as alumina, or silicates of metals like aluminum, calcium, magnesium and cerium,

possesses entirely different properties fromordinary charcoal, in soifar as its catalytic activity is concerned, although in other respects identical with ordinary charcoal. This superior catalytic activity of the charcoal treated in accordance wlthmy invention is developed when it is used as the porous body upon'which the catalytic material, say metallic nickel, active nickel oxid, or the like, is deposited, and is extraordinary' in degree and importance. Thus, while ordinary charcoal or organic carbon even when subjected tomethods of purification is possessed of no more value as a support for an active metal or active metal oxid-than other inert supports, such as pumice or kieselguhr,

and is even inferior to these, charcoal treated may be subjectedto dry distillation in a reb tort. However, I do not limit myself to the use of any particular wood in maklng my active charcoaLasI have obtained good results with both coniferous and deciduous wood. I have also made active charcoal ap-- propriate to the present invention fromcararvzna roe nrnn'oeunarmeores Specification of Letters Patent, Application filed May M, 1914. Serial No. seams.

other organic clear,

charcoal is allowed to cool out of lutlon may be new JERSEY.

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substances, cornstalks and peat. The atmosphere of the retort may be kept under reduced pressure,

or the distilling operation may be expedited by means of a current of superheated'steam passed through the retort, or a current of carbon dioxid gas. It is best not to use too high a temperature in making the charcoal, but it should nevertheless be suificiently high to drive off volatile matter.

After the distillation has progressed until it is substantially complete so that volatile products of decomposition are no longer given off by increased heat, the resulting contact with the air. When entirely cool, it may then be powdered,and saturated with a dilute solution 0' an alkaline silicate; an 8% solution of sodium silicate may be used to advantage, although the strength of the sovaried considerably in either d rection.

The charcoal thus impregnated with silicate should then be heated in a closed retort,

to a dull red heat or a temperature somewhat under a dull red heat. It should then be allowed to cool to atmospheric temperal ture out of contact with air before being re- 7 moved from the retort and may then be treated with a solution of say aluminlun sulfate, alum, or other salt of aluminum. The supportthus prepared may be washed, with water, and coated or impregnated with catalytic :metal, as for instance, nickel, or other catalytic substance, (as, for instance, active oxid of nick l). l Any of the wellknown methods for coatcatalytic metal may be used. If the nickel is obtained by first saturating the active charcoal with a solution of nickel nitrate, and later igniting in the presence of the nitrate, I have found a dilute solution of the i nitrate to give the best results. A good way to 'prepare the catalyzer .is to saturate the active'charcoal with a solution of some nickel salt, then remove the excess nickel solution,

y pressure or filtration, and then treat the active charcoal, coated and impregnated with nickel solution, with an excess of a dilute solution of sodium carbonate or other 10 precipitant, whereby the nickel becomes fixed within andpuponthe active, charcoal in a form insoluble in water. The excess sodium I as, for instance, 55

The catalyzer thus formed may be thrown into oil or fat without being exposed to the air, and the mixture of oil and catalyzer, or fat and catalyzer, may then be used in the hydrogenation of unsaturated oily materials. In some instances, the metallic nickel of my catalyzer may be subjected to mild oxidation, whereby it is converted wholly or partly into a low oxid of nickel, which, while still possessing active catalytic properties is nevertheless comparatively stable when exposed to the atmosphere. This oxidation may be brought about advantageously by passing a current of carbon dioxid, at the temperature of a dull red heat or a temperature somewhat under a dull red heat, over the reduced nickel, whereby a portion of the oxygen of the carbon dioxid is yielded to the nickel to form a low oxid of nickel,which is still stable at that temperature. By keeping the catalyzer, while it is cooling, in contact with carbon dioxid gas the nickel is prevented from taking up oxygen from the air, while the carbon dioxid does not yield its oxygen to the nickel or low oxid of nickel at low temperatures to form other and inactive oxids of nickel.

I can also produce the active low oxid of nickel upon the catalyzer'by allowingthe catalyzer containing metallic nickel to cool, after having reduced the metal, out of contact with the air, preferably in the .presence oi hydro en gas, then exhausting by means of an e cient vacuum pump, all the gas possible from the catalyzer, and then 1n troducing gradually and slowly .air at a low temperature. In this way, only a slight amount of oxidation can take place, at a given time, and without the generation of appreciable heat, and without the presence 0 excess oxygen; until finally, a point is reached when no further oxidation takes place.

Should the hydrogen gas adhering to the catalyzer not be removed or displaced bev fore-air is allowed to come in contact with the catalyzer, the catalytic action of the metallic nickel would cause the hydrogen to combine at once with the oxygen of the air, thus producing enough heat to cause I the metallic nickel of the catalyzer to oxidize to an extent that appreciably diminishes its activity. This same over-oxidation of the catalyzer takes place to a less degree if the catalyzer freed from adhering hydrogen gas is allowed to come in contact with warm air, or if the air is admitted too rapidly.

In case my catalyzer is prepared from active charcoal made by impregnating charcoal with calcium or magnesium compounds,

it is especially desirable to treat the catalyzer with carbon dioxid to avoid an excess of free lime or magnesia.

A catalyzer prepared, as described, from charcoal rendered active by the treatment characteristic of my invention is from ten than catalyzers in other respects'the same but whichare made with the employment of kieselguhr, pumice, or other inert porous support in place of my active charcoal.

Accordingly, I find that where the hydrogenation of oils on a large scale'is carried on, and where an amount of-my improved catalyzer is employed equivalent to the amount customary when ordinary nickel catalyzers are employed, the hydrogenation, which begins at a low temperature proceeds so rapidly by the time the temperature has reached 150 C. that the heat due to rapid absorption of the hydrogen frequently makes it necessary to resort to external cool ing or to a temporary suspension of the operation in order to prevent over-heating. I therefore find it advantageous to operate with a very much smaller amount of my catalyzer than is necessary where the catalytic metal is deposited upon charcoal that has not been made active by the treatment herein described, or which has been deposited upon any other, porous inert material, such as kieselguhr and pumice.

The amount of metal that is necessary to produce good results in operating with my catalyzer is so small that its cost is practically negligible as a factor in the hydrogenation of the oil. So also, the active charcoal that forms a part of my catalyzer is readily made at a low cost. Furthermore, my catalyzer may be used to hydrogenate many successive lots of oil, which fact, coupled with its very low initial cost, makes it practically negligible as an item of expense per pound of oil hydrogenated.

I do not restrict myself to the employment of nickel as the coating or impregnating agent for the active charcoal, although, as indicated, it is highly serviceable and efficient. When nickel is employed',I operate preferably with a catalyzer containing from 2% to 10% of nickel. A catalyzer containing more than 10% of nickel can be used, but the efficiency per unit of nickel becomes less if'10% is materially exceeded.

1. A catalyzer, comprising a catalytic ma terial associated with charcoal impregnated with a catalytically activating morganic compound; substantially as described.

inseam metal associated with charcoal impregnated 'ox id, associated with charcoal impregnated with a catalytically activating inorganic compound; substantially as described.

4. A catalyz'er, comprising nickel, associated with charcoal impregnated with a catalytically activating inorganic compound; substantially as described.

catalyzer, comprising nickel, having a surface coating of a low om'd of nickel, associated with charcoal impregnated with a catalytically acti ating inorganic com.- pound; substantially as described. I

6. A catalyzer, comprising as one of its elements, charcoal impregnated with a-catalytically activating inorganic compound; substantially .18 described.

7. A catalyzer, comprising as one of its elements, charcoal made catalytically active by impregnation with a silicate.

catalyzer, comprising as one of its elements, charcoal made catalytically active by impregnation with a silicate of an earth metal.

9. A catalyzer,

comprising as one of its elements, charcoal made catalytically active by impregnation with aluminum silicate.

10. A catalyzer,

comprising as one of its elements, charcoal impregnated with a catalytically activating oxygen compound of aluminum.

In testimony whereof I afix my slgnature, in presence of two witnesses.

MARTIN HILL ITTNER. 

